High pressure polymerization process for ethylene-1-chloro-1-fluoroethylene copolymers



William R. Richard, In, Dayton, santo Chemical Company, St. tion of Delaware Ohio, assignor to Mon- Louis, Mo., a corpora- No Drawing. Application November 28, 1952, Serial No. 323,123

6 Claims. (Cl. 260-817) This invention relates to the polymerization of ethylene at high pressures in admixture with minor amounts of 1- chloro-1-fluoroethylene in an aqueous medium. In a specific aspect the invention efiects improvement in the characteristics of normally solid polyethylene prepared at high pressure in the presence of water, by the inclusion of small amounts of 1 chloro 1 fluoroethylene as a comonomer with the ethylene. In another aspect the invention relates to the production of a copolymer having the general characteristics of polyethylene, i. e., normally solid, waxy in feel, showing some crystallinity by X-ray diffraction, yet improved in physical properties by inclusion of relatively small proportions of 1 chloro 1- fluoroethyiene units in the polyethylene molecule.

It has long been known to subject ethylene to polymerization at high pressures of the order of at least 500 atmospheres and often up to 40,000 or 50,000 pounds per square inch, with or Without the use of small amounts of oxygen or organic peroxide catalysts, thereby producing a normally solid waxy polymer of high molecular weight ranging from 6,000 up to 20,000 or 40,000 and showing the presence of crystalline material by X-ray ditfraction analysis. Material prepared in this manner and having these general properties is now commonly termed polyethylene and is a very important product in the plastics industry. It was also suggested long ago to employ various unsaturated materials as comonomers along with the ethylene in high pressure polymerization.

The production of a polyethylene having sufiiciently good physical properties to make it a saleable commercial product is not easy. The molecular Weight, the presence or absence of cross-linking and branching, the stability of the product toward oxidation and other degradation, are all sensitive to fairly minor variations in reaction conditions. Even the best commercial polyethylenes leave something to be desired in their physical properties. it would be of great practical importance to find a simple means of improving such properties, and particularly of permitting the production of commercial grade polyethylene under reaction conditions which do not ordinarily give a satisfactory commercial product.

Attempts have been made to solve some of these problems by employing added liquid organic reaction media, for example benzene or tertiary butyl alcohol, which result in modifying the polymer and making it more proc essable. However, such organic liquids are expensive, their recovery and reuse are expensive, and it is exceedingly difiicult to remove them entirely from the polymer product. Employment of Water as a. reaction medium, although advantageous for heat removal and catalyst metering, has been unsuccessful in producing at moderate reaction temperatures a product which is satisfactory from the commercial viewpoint. Thus, as described in U. S. Patent No. 2,542,783, polymerizing ethylene in an aqueous emulsion at temperatures such as 40 to 120 C. is not satisfactory, the polymers being of poor mechanical properties and having poor flow characteristics. As further stated in said patent, polymerizing at above 120 C. is not satisfactory unless, in accordance with the process described in that patent, an added water-soluble ttes Patent O salt of a high molecular weight polymer of a carboxylic acid is used. Thus, it is desirable to provide some means of efiecting production of solid polyethylene-type materials by polymerizing ethylene in the presence of water yet employing reasonably low temperatures, particularly temperatures below the 200 C. principally employed in the process of the cited patent.

An object of this invention is to provide improved polyethylene-like materials. Another object of the invention is to provide improved processes for the polymerization of ethylene at high pressures in the presence of Water. A further object is to provide a comonomer for ethylene which, when used in relatively minor amount along with the ethylene during high pressure polymerization with an aqueous reaction medium greatly improves the physical properties of resulting normally solid polymers. Another object is to provide a process for making a polyethylene-type product which mills easily and is easily molded in conventional equipment. Another object is to provide a polymer which does not become brittle and grainy on reprocessing. Further objects and advantages of the invention will be apparent, to one skilled in the art, from the accompanying disclosure and dis,- cussion.

In accordance with this invention in preferred embodiment, a monomeric material comprising ethylene and 1- chloro-l-fiuoroethylene is subjected to copolymerization at an elevated pressure, preferably at least 5,000 pounds per square inch, in the presence of an aqueous reaction medium, under conditions of temperature and catalyst resulting in the production of normally solid polymer. Ordinarily the monomeric mixture comprises from to 70 weight percent ethylene and from 5 to 30 percent 1- chloro-l-fiuoroethylene. However, larger proportions of the latter can be employed, for example '70 to 55 Weight percent ethylene and 30 to 45 Weight percent l-chloro-lfluoroethylene, and in such instances it is preferred to effect the polymerization at a pressure above 20,000 pounds per square inch and particularly above 40,000 pounds per square inch. Most frequently l-chloro-lfluoroethylene makes up not over 20 percent of the monomeric material. In accordance with a preferred aspect of my invention, ethylene and l-chloro-l-fiuoroethylene (sometimes called vinylidene chlorofluoride) are copolymerized in the presence of water and in the absence of a liquid organic reaction medium under high pressure to form a polymer which has physical properties superior to those of polyethylene made from only ethylene in the presence of water and under the same conditions. This is surprising inasmuch as vinyl fluoride and vinylidene fluoride copolymerize with ethylene under the same conditions to form cross-linked materials.

The polymerization can be carried out at temperatures Within a fairly broad range, which is preferably 35 C. to 125 C. Higher temperatures tend to result in a dis colored product, perhaps by decomposition of vinylidene chlorofluoride units in the polymer molecules. A tem perature suiliciently high Within the operative range should be used to give a reasonable reaction rate. The preferred range is 50 to C. It is an advantage of this invention that such moderate temperatures can be used and yet polymers are produced that are readily processable as opposed to the unduly tough and grainy polymers made from ethylene at conditions identical except for the absence of vinylidene chlorofluoride.

While I consider a pressure of at least 5,000 pounds per square inch very desirable in carrying out my invention, pressures of at least 15,000 pounds per square inch are usually employed and much higher pressures are also suitable, for example above 40,000 pounds per square inch and up to say 200,000 pounds per square inch and even higher. A monomeric mixture of ethylene and 3 l-chloro-l-fluoroethylene containing less than 3 percent of the latter results in little significant improvement of product over that with ethylene alone. Proportions of l-chloro-l-fluoroethylene within the range of from S to.

4 g tageously introduced into the reaction dissolved or suspended in the water. It will of course be understood that one catalyst will not necessarily be the full equivalent of another in all respects.

30 percent ordinarily result in the greatest improvement 5 The process of this invention can be carried out batchof product. Amounts of l-chloro-l-fluoroethylene above W156 commuously- The reaction mixture m y c n 25 percent in the total monomeric material tend to give 05 W Y F Y d taly t, a h product when polymerized at pressures below or it may also include small amounts of other monomeric 0,000 pounds per square inch. However, this somewh materials In the case of a continuous reaction, the reundesirable etfect can be compensated to an appreciable 1O acilon mlfitufe pr ferably passed through an elongated extent b employment f pressures above 9% Pounds coil provided with meansfor removing heat of reaction squal-e i and particularly so by pressures above and capable of withstand ng the high pressure required. 40,000 pounds per square inch. Those skilled in the art, I Prefer to P l f 9 9 Parts of Water PF having had the benefit of the present disclosure, will u Parts cf W sufiiclef'lt aglfatlofl readily choose a combination of monomer proportion and 9 can be supplied, as y fl 1I1g a batch of reaction m xture pressure as well as other reaction conditions best suited or by Passing Continuous Stream of reaction. to give a product having Characteristics dash-ed fer a through a reaction zone atturbulent flow conditions, to particular use. In accordance with the invention, 1 result in intimate contact of water, monomers and cataethylene-type polymers can be made which do not become 7 IYSY- Known susPendmg or remulslfymg agfints can he brittle or grainy on reprocessing, which have good low L0 added to Produce f f a latex pl'oduct' Umeacted temperature flexibility and which have high tensile elonmonQmenc mammal recwel'ed and recyckd to the gation yet satisfactory tensile strength. The preferred reaction? V effects on the polyethylene-like product are not found The Q 111 its bfoadest f 15 not dBPaTte-d if the Weight of l-chloro-1-fiuoroethylene in the mono- T fmm by P relanvely mmol' a u of other men'c mixture of same with ethylene becomes larger than mwfgmfans i' capable of entenflg i the l" the Weight of the ethylflm merlzation reaction. Thus, vinyl chloride, vinyl acetate, While ethylene can be copolymerized with l-chloro-l- Propylene styrene f othef i- Orgamc fluoroethylene Within the broad aspects of the invention Pounds a be used f rafigmg up to a few F without the use of an added catalyst, it is much preferred cent T1113 of course W111 affect Polymer lf to employ suficient catalyst to give a reasonable reaction but the amount can be kept sufiiclgnfly low to Tetam the rate. Suitable catalysts are of the freeqadical promoting advantageous results f the use 3' type, principal amhhg Which are perhxidfitvpe polymer ene as a comonomer with ethylene in the aqueous med um ization catalysts, and azo-type polymerization catalysts. high pressure production oi polyethylene-type materials. Those skilled in the art are now fully familiar with a foiiowmg l Submltted exemplify large number f peroxide tyhe polymerization catalysts the 1nvent1on. However, 1t will be understood that the and a suitable one can readily be chosen by simple trial. exact p p t ns, conditions and procednres descr bed such catalysts can be inorganic or Organic, the latter are not to be taken to limit the invention 11'] its broadest having the general formula ROOR" wherein R is an aspectsorganic radical and R" is an organic radical or hydrogen. 40 M 1 These COmPOUHdS are broadly tanned peroxides, and in The following materials were charged to a stainless a more specific sense are hydroperoxides when R" is steel high pressure reactor: hydrogen. R and R" can .be hydrocarbon radicals or Grams organic radicals substituted with a great variety of subl-QhlorO-l-fiudrcethylene 9 stituents. By way of example suitable peroxide-type Erh k 91 catalysts include benzoyl peroxide, tertiary butyl peroxide, W t 150 tertiary bntyl hydroperoxide, diacetyl peroxide, diethyl Pu f .N1 Q1 peroxycarbonate, cumene hydroperoxide, among the or- 1 a,at;zodhsobutymnimlel game peroxides; hydrogen peroxide, potassium persulfate, perborates and other peroxide-type catalysts. The azo- The bc'mb Was heated to Pressured to 16,000 type polymerization catalysts are also well-known to those Pounds P Square inch, and Polymerization allowed to skilled in the art. These are characterized by the presmmimle for 16 hourscoflvel'siflfl t0 P y Was 45 once in the molecule of the group -N=N-; the dangling P valences can be attached to a wide variety of organic The Product Was 7 3 PIOCBSSed P a 110i 111111, and radicals, at least one however preferably being attached M was s y molded l f l l l y y to a tertiary carbgn atom B way f example of i ene made under the same conditlons from ethylene alone ble azo-type catalysts can be mentioned a,a'-azodiisobucould not be mlued molded f to the Presence of tyronitrile, diazoaminobenzene, azobis (diphenylmethlarge amounts of Cross-111mm materialsane), and u,ct'aZObiS ouy dimethylvaleronitrile. The EXAMPLE 2 peroxy-type or azo-type polymerization catalyst 18 used r in small but catalytic amounts, which are generally not Difierences between polyethylene and ethylene-v1nyli in excess of 1 percent by weight based upon the monodene chlorofiuoride copolymer made in an aqueous medimeric mixture. A suitable quantity is often in the range um at similar conditions are apparent from the following of 0.05 to 0.5 percent by weight. The catalyst is advantables. Table I POLYMEBIZATION Run Monomer Catalyst Te rlpu gressfl Medium Tag-e, Pgaceggt A 6U ethy1 ene+10 0.1% Porotor N-.. 16, 000 Water 16 64 B 50 g ;iene do on 16,000 do.. 16 es 1 VOF is l-ohloro-l-fluoroethylene.

Table [1 EVALUATION Clash Berg Tensile Tensile Material Strength, Elong., Remarks p. s. i. Percent T2000, Stlfilex T1, 0. 0. Range,

Gopolymer A 1, 250 800 -36.3 +58. 5 94. 8 Remolds and processes well. Material representative 1,980 47 -8.5 +107 115.5 Poor processing characterisof conditions used in ties. uetility lowered by Bun B. processing. Commercial polyethyl- 1, 800 500 86.0 +86. 122 Remolds and processes well.

ene.

These data show adequate tensile strength and excellent elongation of the product made in accordance with the present invention, the latter being superior to that of the commercial polyethylene. It must be borne in mind that the conditions for the copolymerization were characteristic of those which produced a polyethylene unsuited for commercial use. The invention gave a product of excellent low temperature flexibility as shown by the Clash- Berg Tr value.

While the invention has been described with particular reference to various preferred embodiments thereof, it will be appreciated that numerous modifications and variations are possible without departing from the invention.

I claim:

1. In the production of normally solid polymers by high pressure polymerization of ethylene in aqueous media, the improvement which comprises subjecting from 55 to 95 parts by Weight ethylene and from 45 to parts by weight l-chloro-l-fiuoroethylene to copolymerization in the presence of at least 10 parts by weight water as the sole reaction medium, at a temperature within the range of 35 to 125 C. and a pressure of at least 5,000 pounds per square inch with the further proviso that said pressure is at least 20,000 pounds per square inch when said l-chloro-l-fiuoroethylene exceeds 25 parts by weight, and recovering resulting easily processed high copolymer.

2. The catalytic copolymerization of from 80 to 95 parts by Weight ethylene with from to 5 parts by weight l-chloro-l-fiuoroethylene at a temperature within the range of 35 to 125 C. and a pressure of at least 15,000 pounds per square inch in the presence of at least 10 parts water as the sole reaction medium.

3. The catalytic copolymerization of from 55 to 70 parts by weight ethylene with from 45 to 30 parts by weight l-chloro-l-fiuoroethylene at a temperature within the range of 35 to 125 C. and a pressure of at least 40,000 pounds per square inch in the presence of at least 10 parts water as the sole reaction medium.

4. A process which comprises polymerizing in the presence of from 10 to 500 parts by weight water as the sole reaction medium, 100 parts by weight of a monomeric mixture consisting of a major part by weight of ethylene and a minor part by weight of l-chloro-l-fluoroethylene with a catalyst selected from the group consisting of azo and peroxy polymerization catalysts, at a temperature within the range of 35 to 125 C. and a pressure of at least 5,000 pounds per square inch with the further proviso that said pressure is at least 20,000 pounds per square inch when the l-chloro-l-fluo-roethylene content of said monomeric mixture exceeds 25 percent.

5. A process according to claim 4 wherein said catalyst is oz,0t'-21Z0diiSOblltYrOIlitI'ilG.

6. A process which comprises subjecting a monomeric material consisting of from to parts by weight ethylene and from 20 to 5 parts by Weight l-ch1oro-1- fluoroethylene to catalytic copolymerization in the presence of from 10 to 500 parts by Weight water as the sole reaction medium, at a pressure of at least 15,000 pounds per square inch, and at a temperature of from 50 to C., and recovering resulting normally solid copolymer having a tensile elongation in excess of 500 percent and a tensile strength in excess of 1,200 pounds per square inch and being readily processed on the hot mill.

References Cited in the file of this patent UNITED STATES PATENTS 1,952,116 Bridgman et a1 Mar. 27, 1934 2,397,260 Hanford et al Mar. 26, 1946 2,409,996 Roedel Oct. 22, 1946 2,449,489 Larson Sept. 14, 1948 2,467,234 Sargent et al Apr. 12, 1949 2,468,054 Ford Apr. 26, 1949 2,479,367 Joyce et al. Aug. 16, 1949 2,471,959 Hunt May 31, 1949 

1. IN THE PRODUCTION OF NORMALLY SOLID POLYMERS BY HIGH PRESSURE POLYMERIZATION OF ETHYLENE IN AQUEOUS MEDIA, THE IMPROVEMENT WHICH COMPRISES SUBJECTING FROM 55 TO 95 PARTS BY WEIGHT ETHYLENE AND FROM 45 TO 5 PARTS BY WEIGHT 1-CHLORO-1-FLUOROETHYLENE TO COPOLYMERIZATION IN THE PRESENCE OF AT LEAST 10 PARTS BY WEIGHT WATER AS THE SOLE REACTION MEDIUM, AT A TEMPERATURE WITHIN THE RANGE OF 35 TO 125*C. AND A PRESSURE OF AT LEAST 5,000 POUNDS PER SQUARE INCH WITH THE FURTHER PROVISO THAT SAID PRESSURE IS AT LEAST 20,000 POUNDS PER SQUARE INCH WHEN SAID 1-CHLORO-1-FLUOROETHYLENE EXCEEDS 25 PARTS BY WEIGHT, AND RECOVERING RESULTING EASILY PROCESSED HIGH COPOLYMER. 